US4590057A - Process for the generation of chlorine dioxide - Google Patents
Process for the generation of chlorine dioxide Download PDFInfo
- Publication number
- US4590057A US4590057A US06/651,167 US65116784A US4590057A US 4590057 A US4590057 A US 4590057A US 65116784 A US65116784 A US 65116784A US 4590057 A US4590057 A US 4590057A
- Authority
- US
- United States
- Prior art keywords
- chlorine
- chlorine dioxide
- reaction
- metal chlorite
- chlorite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/023—Preparation from chlorites or chlorates
- C01B11/024—Preparation from chlorites or chlorates from chlorites
Definitions
- This invention relates to a process for the production of chlorine dioxide.
- Chlorine dioxide is utilized in a variety of processes, including a large number of bactericidal applications, especially in the fields of water treatment and odor abatement. Its usage is continuing to grow for many reasons. Due to the unstable nature of gaseous chlorine dioxide when compressed, it is necessary to produce chlorine dioxide on site rather than to produce it at a plant and ship it for usage when and where needed.
- the relatively concentrated aqueous metal chlorite solution and the oxidizing agent are allowed to mix and react in the premix chamber prior to any dilution as, for example, by water or other fluid flowing through the venturi eductor to deliver the generated chlorine dioxide to storage or utilization.
- any diluent for example water
- the gaseous chlorine stream contains some bleed water in an amount below that which would significantly dilute the reactants and thereby have a quenching effect on the reaction.
- the presence of bleed water prevents a buildup of metal chloride on the chlorine inlet to the premix chamber.
- the process of this invention consists of a method for the generation of chlorine dioxide comprising the essentially instantaneous reaction of a relatively concentrated aqueous solution of a metal chlorite and gaseous chlorine in a reaction zone sized to permit substantially instantaneous contact of the reactants and wherein the gaseous chlorine contains bleed water in an amount below that which would significantly dilute the reactants and thereby have a quenching effect on the reaction.
- the presence of bleed water in the gaseous chlorine prevents the buildup of deposits of solid metal chloride on the chlorine inlet to the reaction zone.
- this invention consists of a process for the generation of chlorine dioxide comprising the steps:
- the instant invention thus provides a process for the generation of chlorine dioxide by the essentially instantaneous reaction of a relatively concentrated aqueous solution of a metal chlorite and an oxidizing agent, preferably gaseous chlorine, in a reaction zone sized to permit substantially instantaneous contact of reactants.
- the invention is characterized by the absence of a buildup of solid metal chloride deposits on the chlorine inlet to the reaction zone.
- the reaction is carried out in a generator having a mix and dwell premix chamber interconnected with a source of vacuum, preferably a venturi.
- the relatively concentrated aqueous metal chlorite solution and the gaseous chlorine are allowed to mix and react in the premix chamber prior to any dilution as, for example, by water or other fluid flowing through the venturi eductor to deliver the generated chlorine dioxide to storage or utilization.
- the gaseous chlorine contains bleed water in an amount below that which would significantly dilute the reactants and thereby have a quenching effect on the reaction. The presence of bleed water prevents a buildup of metal chloride on the chlorine inlet to the premix chamber.
- FIG. 1 illustrates one embodiment of the apparatus of the present invention wherein a relatively concentrated aqueous metal chlorite solution and gaseous chlorine are employed for the generation of chlorine dioxide.
- FIG. 2 illustrates an alternate configuration for the premix chamber of FIG. 1.
- a process for the preparation of chlorine dioxide which process employs a reaction vessel comprising a vacuum eductor having a "T" shaped premix chamber in fluid communication with the low pressure zone, i.e., beyond the throat of the venturi of the eductor.
- a "T" shaped premix chamber includes inlet means for an aqueous metal chlorite solution and the gaseous chlorine at opposite ends of the portion of the "T" normal to the venturi throat, a dwell chamber or contact area in fluid comminication therewith terminating in an outlet to the low pressure zone beyond the throat of the venturi for admixture with water being drawn through said venturi for mixture with the chlorine dioxide reaction product of metal chlorite and chlorine.
- Included in the system are means for introducing bleed water into the pipe conducting chlorine into the premix chamber.
- FIG. 2 While a "T" shaped premix chamber is preferred due to ease of availability in the marketplace, other configurations such as that of the embodiment of FIG. 2 may also be employed. These configurations also feature inlet ports and lines in a main body section and a contact zone, also in said main body section. The chamber is in fluid communication with an eductor for removing generated chlorine dioxide and transporting it to storage or utilization.
- the chlorine dioxide generation system of this invention is best understood by reference to the accompanying drawings.
- generator 100 designates the chlorine dioxide generator in general
- generator 100 is shown attached by suitable means (not illustrated) to mounting board 23.
- the apparatus comprises the combination of an eductor 11 with a premix chamber 20 forming generator 100.
- Eductor 11 includes an inlet 12 for the delivery of generated chlorine dioxide by water 45 which passes through said eductor 11.
- the chlorine dioxide dissolved in water is designated by arrow A.
- This combination is delivered through other piping (not shown) a short distance in concentrated form to water or other material to be treated, for example, waste in a sewage plant.
- the concentrated end product is shown by arrow A exiting eductor outlet 67.
- premix chamber 20 which may be mounted as desired to mounting board 23, either alone or, as shown here, below the throat but always in direct fluid communication with low pressure zone 65.
- the premix chamber is also called a prereaction chamber.
- T 20 includes inlet ports 41 and 31 for the introduction of reactants.
- the ports are each sealed off from the environment by check valves 41A and 31A, respectively.
- a contact area 21 and an outlet 61 are also provided.
- Outlet 61 is in fluid communication with low pressure zone 65 of eductor 11.
- Chlorite ion source 18 is connected by pipeline 28 to inlet port 41 through rotometer 16.
- Gaseous chlorine source 17 is connected in like manner via pipe 29 and rotometer 15 to port 31.
- Bleed water source 50 is connected by pipe 51 to pipe 29 through rotometer 53 just upstream from inlet port 31.
- Check valve 52 is located on pipe 51.
- FIG. 2 is found an alternate embodiment of the premix chamber shown in FIG. 1.
- 301 designates the chlorine dioxide generator in general
- generator 301 is shown attached by suitable means (not illustrated) to mounting board 23.
- the premix chamber of FIG. 2 is shaped like an inverted letter "F". Since like numbers denote like parts, certain items will not be redescribed.
- the embodiment of FIG. 2 features premix chamber 80 wherein the contact area 71 denotes the location in the chamber wherein incoming ingredients 28 and 29 mix in the absence of sufficient water to quench the reaction to thereby react and form chlorine dioxide.
- the present invention provides an improvement over my invention described in U.S. Pat. No. 4,247,531.
- the chlorine gas stream contains bleed water which prevents the buildup of metal chloride deposits on the chlorine inlet to the premix chamber.
- water 45 is shown as the vacuum forming diluent, any fluid which does not react with and which is compatible with chlorine dioxide may be employed.
- an inert gas such as nitrogen can be employed to remove the reaction products, primarly chlorine dioxide, to a location of either short term storage or actual end use.
- threads 69 are depicted to show that it is within the scope of the invention to attach threaded pipes or lines from sources of the reactants to the female threads 69 of the premix chamber 80.
- Check valves 31A and 41A are also employed.
- an ingredient e.g., a concentrated aqueous metal chlorite solution
- the ingredient moves through a section of the premix chamber 80 along with chlorine to the contact zone, a location where all of the reactants can mix and react together to form chlorine dioxide.
- the location of contact area 71 is seen to be upstream from exit 61 into the eductor and downstream from the point of entrance of the reactants being employed.
- FIG. 2 While not shown in FIG. 2 for ease of understanding, the use of rotometers or other valves is contemplated for this embodiment as well as that of FIG. 1.
- water 45 or some other fluid should be employed to move the chlorine dioxide from the contact area through the eductor.
- any compatible fluid, liquid or gaseous, that will not react with the chlorine dioxide may be employed.
- steam or nitrogen may be used.
- the flow rate of the moving fluid 45 should be such that for a given feed rate of reactants, the moving fluid is able to remove all of the chlorine dioxide generated so that a buildup of product is avoided.
- the flow rate should be such as to exhaust and absorb substantially all of the chlorine dioxide. This rate is readily determinable since it is known that the solubility of chlorine dioxide in water at room temperature is about 2,900 ppm.
- an operable vacuum range for any of the embodiments of this invention is within the range of about 5 to about 30 inches of mercury. Accordingly, it is within the skill of the art to adjust the flow through the eductor to remove the chlorine dioxide product as generated.
- Altering the shape of the premix chamber by lengthening the entry pipes is of no benefit as the reactants are kept apart in this zone. Lengthening the contact zone can be beneficial up to a certain point as the high conversion rates associated with this process are due to the ability of the reactants to premix in the substantial absence of any other fluid in amounts to significantly dilute the reactants and thereby have a quenching effect on the reaction. Lengthening the contact zone beyond that required for instantaneous reaction is unnecessary. Thus, conversion rates of from about 72% to about 97%, depending on the absence or presence of packing which serves to increase exposed surface area through mixing and to slow down the movement of the reactants through the reaction zone, are available by the practice of the instant invention. This compares to conversions of about 40% in state of the art column type reactors when high pH water and/or low chlorine dioxide generation rates are used.
- the premix chamber of the apparatus of this invention may include a contact zone that varies from less than about 1 inch to 3 feet or more.
- a contact zone that varies from less than about 1 inch to 3 feet or more.
- the premix chamber of this invention is designated as such because the reactants are given a chance to react, prior to mixing with any other fluid which may dilute the reactants sufficiently to quench the reaction.
- a diluting fluid usually water
- Applicant has found that by removing the product by the eductor, the buildup of chlorine dioxide in a confined volume can be avoided as is deemed essential; yet by use of the instant invention, high conversion rates are achievable.
- eductor 11 includes an inlet 61 which is also the outlet from the premix chamber since they together form the contiguous apparatus of this invention.
- the two parts of the apparatus are in fluid communication for the removal of generated chlorine dioxide.
- the eductor includes a horizontally disposed inlet section 12 having a nozzle 63 therein.
- the front tip of nozzle 63 is located substantially centrally above inlet 61 and normal thereto. Spaced apart from said tip, and downstream therefrom, is a diffuser or outlet 67. Diluted or dispersed product is discharged from eductor 11 to a place of utilization or storage as designated by the letter A showing outflow.
- any eductor compatibly sized with the premix chamber may be employed as long as it can remove the product as generated.
- the metal chlorite employed as a reactant in the process of this invention may be any water-soluble metal chlorite.
- alkali metal chlorites such as lithium chlorite, sodium chlorite, and potassium chlorite and alkaline earth metal chlorites such as calcium chlorite, barium chlorite, and magnesium chlorite.
- Alkali metal chlorites are preferred with sodium chlorite being most preferred.
- a critical feature of this invention is that, compared to the prior art, the aqueous metal chlorite solutions of this invention are relatively concentrated. It is largely due to the relatively high concentrations of the metal chlorite solutions and the use of nonhydrolyzed chlorine gas that the substantially instantaneous reaction is achieved.
- the use of nonhydrolyzed gaseous chlorine is in contrast to many prior art processes where chlorine is first dissolved in water and becomes hydrolyzed to hypochlorous acid. In such prior art processes, chlorine is not present in the reaction zone.
- Prior art metal chlorite solutions have concentrations of the order of about 1 weight percent metal chlorite.
- aqueous metal chlorite solutions of this invention contain about 5 weight percent to about 35 weight percent of metal chlorite and preferably about 10 weight percent to about 25 weight percent of metal chlorite. Concentrations of metal chlorite below about 5 weight percent in the reactor result in some quenching of the reaction, and concentrations of about 1 weight percent cause the reaction to proceed very slowly.
- the ratio of aqueous metal chlorite solution to gaseous chlorine is ideally such that the metal chlorite and the chlorine reactants are present in approximately stoichiometric amounts. In some cases, it can be desirable to have an excess of chlorine to drive the reaction to completion. The excess chlorine appears in the generator effluent.
- the gaseous chlorine contains bleed water.
- the presence of the bleed water prevents any tendency for solid metal chloride deposits to build up on the chlorine inlet to the premix chamber.
- the amount of bleed water in the gaseous chlorine is just enough to prevent a buildup of solid metal chloride on the chlorine inlet but not enough to significantly dilute the reactants to thereby have a quenching effect on the reaction.
- the amount of bleed water in the gaseous chlorine is broadly within the range of about 0.3 to about 10.0, and preferably within the range of about 0.5 to about 5.0 grams of bleed water per gram of chlorine.
- the feed rates of the reactants will vary depending on several factors.
- the feed rates will depend on the size of the premix chamber, the presence or absence of packing in the premix chamber, and the capacity of the eductor as well as the concentration of the metal chlorite solution.
- the feed rate of sodium chlorite solution is about 0.1 to about 50 gallons per hour; and the feed rate of gaseous chlorine containing bleed water is such as to provide about half a pound of chlorine per hour; for each pound of sodium chlorite in the solution that is fed into the premix chamber per hour.
- the effluent was found to contain 1117.5 mg./l. of chlorine dioxide, 14.6 mg./l. of chlorite ion, 6.7 mg./l. of chlorate ion, and 3.2 mg./l. of chlorine. The yield of chlorine dioxide was therefore 98.3%.
- the generator was then allowed to run an additional straight 48 hours. There was no buildup of solid sodium chloride on the chlorine inlet to the reaction chamber. The foregoing was repeated in the absence of bleed water in the chlorine feed. A deposit of solid sodium chloride built up on the chlorine inlet to the reaction chamber, causing the chlorine feed rate to drop substantially.
- Example 1 was repeated several times with the exception that the amount of bleed water in the chlorine stream was varied each time. The results are set forth below.
- the instant invention provides a process for the generation of chlorine dioxide by the essentially instantaneous reaction of a relatively concentrated aqueous solution of a metal chlorite and gaseous chlorine.
- the reaction is carried out in a generator having a mix and dwell premix chamber interconnected with a source of vacuum, preferably a venturi.
- the relatively concentrated aqueous metal chlorite solution and the gaseous chlorine are allowed to mix and react in the premix chamber prior to any dilution as, for example, by water or other fluid flowing through the venturi eductor to deliver the generated chlorine dioxide to storage or utilization.
- the process is characterized in that the chlorine feed contains bleed water in an amount below that which would significantly dilute the reactants and thereby have a quenching effect on the reaction. The presence of bleed water prevents a buildup of metal chloride on the chlorine inlet to the premix chamber.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/651,167 US4590057A (en) | 1984-09-17 | 1984-09-17 | Process for the generation of chlorine dioxide |
AU47503/85A AU574224B2 (en) | 1984-09-17 | 1985-09-16 | Generation of chlorine dioxide |
CA000490836A CA1228714A (en) | 1984-09-17 | 1985-09-16 | Process for the generation of chlorine dioxide |
JP60205141A JPS61183104A (ja) | 1984-09-17 | 1985-09-17 | 二酸化塩素を発生させる方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/651,167 US4590057A (en) | 1984-09-17 | 1984-09-17 | Process for the generation of chlorine dioxide |
Publications (1)
Publication Number | Publication Date |
---|---|
US4590057A true US4590057A (en) | 1986-05-20 |
Family
ID=24611829
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/651,167 Expired - Lifetime US4590057A (en) | 1984-09-17 | 1984-09-17 | Process for the generation of chlorine dioxide |
Country Status (4)
Country | Link |
---|---|
US (1) | US4590057A (pt) |
JP (1) | JPS61183104A (pt) |
AU (1) | AU574224B2 (pt) |
CA (1) | CA1228714A (pt) |
Cited By (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5258171A (en) * | 1990-03-28 | 1993-11-02 | Ashland Oil, Inc. | Method of producing chlorine dioxide in a gaseous stream and apparatus therefor |
US5639559A (en) * | 1995-07-25 | 1997-06-17 | Rio Linda Chemical Company, Inc. | Preparation of chlorite |
US5707546A (en) * | 1991-06-17 | 1998-01-13 | Rio Linda Chemical Co., Inc. | Generation and storage of chlorine dioxide in a non-aqueous medium |
US5853689A (en) * | 1997-02-11 | 1998-12-29 | Klatte; Fred | Method for producing chlorine dioxide by activating an impregnated zeolite crystal mixture, and mixtures for performing such method |
US5855861A (en) * | 1996-02-23 | 1999-01-05 | Water Technologies Limited | Method and apparatus for making aqueous chlorine dioxide |
US5885543A (en) * | 1997-02-11 | 1999-03-23 | Klatte; Fred | Method for producing chlorine dioxide using calcium chloride impregnated zeolite or aqueous calcium chloride |
WO1999051332A1 (en) * | 1998-04-02 | 1999-10-14 | Vulcan Chemical Technologies, Inc. | Chlorine dioxide generator |
US6051135A (en) * | 1996-02-23 | 2000-04-18 | Water Technologies Limited | Apparatus for making aqueous chlorine dioxide and apparatus for treating water with aqueous chlorine dioxide |
US6174508B1 (en) | 1997-02-11 | 2001-01-16 | Fred Klatte | Method of producing chlorine dioxide using sodium chlorite and a water-retaining substance impregnated in zeolite or in aqueous solution |
US6322768B1 (en) * | 1998-09-29 | 2001-11-27 | International Paper Company | Recovery of chlorine dioxide from gas streams |
US6343653B1 (en) | 1999-08-27 | 2002-02-05 | John Y. Mason | Chemical injector apparatus and method for oil well treatment |
US20020061263A1 (en) * | 2000-11-22 | 2002-05-23 | Taylor Rodney D. | Apparatus and methods for efficient generation of chlorine dioxide |
US6431279B1 (en) | 2000-07-14 | 2002-08-13 | Jacam Chemicals, L.L.C. | Process for in situ generation of chlorine dioxide in oil and gas well formations |
US6436345B1 (en) | 2001-03-23 | 2002-08-20 | Chemtreat, Inc. | Method for generating chlorine dioxide |
US6468479B1 (en) | 2000-08-11 | 2002-10-22 | Sabre Oxidation Technologies, Inc. | Chlorine dioxide generator |
US20030138371A1 (en) * | 2002-01-18 | 2003-07-24 | Cdg Technology, Inc. | Method and apparatus for generating gaseous chlorine dioxide-chlorine mixtures |
US20030203827A1 (en) * | 2002-04-30 | 2003-10-30 | Cooper Andrew J. | Method of simultaneously cleaning and disinfecting industrial water systems |
US20030229422A1 (en) * | 2002-06-11 | 2003-12-11 | Vulcan Chemicals | Chlorine dioxide generation systems |
US20040051080A1 (en) * | 2002-09-13 | 2004-03-18 | Ica Trinova, Llc | Composition and method for producing carbon dioxide |
US6716354B2 (en) | 2001-03-08 | 2004-04-06 | Cdg Technology, Inc. | Methods of treating water using combinations of chlorine dioxide, chlorine and ammonia |
US20050058591A1 (en) * | 2000-02-22 | 2005-03-17 | Gerald Cowley | Chlorine dioxide generator |
US20050189081A1 (en) * | 2003-12-23 | 2005-09-01 | M-I L.L.C. | Device and methodology for improved mixing of liquids and solids |
US20060021872A1 (en) * | 2004-07-29 | 2006-02-02 | Pureline Treatment Systems, Llc | Chlorine dioxide solution generator |
US20060034750A1 (en) * | 2004-08-11 | 2006-02-16 | Water Technologies Limited | Chlorine dioxide generator and associated methods |
US20060068029A1 (en) * | 2004-05-17 | 2006-03-30 | Mason John Y | Method of treating with chlorine dioxide |
US20060120928A1 (en) * | 2004-11-12 | 2006-06-08 | William Annacone | Chlorine dioxide generator |
US7273585B1 (en) * | 2000-06-19 | 2007-09-25 | White James M | Biological fluid disposal system |
US20080032905A1 (en) * | 2006-08-02 | 2008-02-07 | Iverson Carl E | Disinfecting/mineral treating composition and methods |
US20110052480A1 (en) * | 2002-06-11 | 2011-03-03 | Edward Max Martens | Chlorine dioxide generation systems and methods |
US20110129388A1 (en) * | 2008-07-25 | 2011-06-02 | Siemens Water Technologies Corp. | Chlorine Dioxide Generation Systems and Methods |
WO2013050774A2 (en) | 2011-10-05 | 2013-04-11 | Paradigm Flow Services Limited | Fire main cleaning apparatus and method |
US8992893B2 (en) | 2011-04-19 | 2015-03-31 | Arms Pharmaceutical, Llc | Method of inhibiting harmful microorganisms and barrier-forming composition therefor |
US9382116B2 (en) | 2013-01-10 | 2016-07-05 | Ica Trinova, Llc | Mixtures for producing chlorine dioxide gas in enclosures and methods of making the same |
WO2016140772A1 (en) * | 2015-03-02 | 2016-09-09 | The Chemours Company Fc, Llc | Method for treating water with chlorine dioxide |
US10308533B2 (en) | 2013-03-15 | 2019-06-04 | Sabre Intellectual Property Holdings Llc | Method and system for the treatment of water and fluids with chlorine dioxide |
US10442711B2 (en) | 2013-03-15 | 2019-10-15 | Sabre Intellectual Property Holdings Llc | Method and system for the treatment of produced water and fluids with chlorine dioxide for reuse |
US10850981B2 (en) | 2017-04-25 | 2020-12-01 | Ica Trinova, Llc | Methods of producing a gas at a variable rate |
US11130677B2 (en) | 2017-03-24 | 2021-09-28 | Ecolab Usa Inc. | Low risk chlorine dioxide onsite generation system |
US11225421B2 (en) | 2017-08-17 | 2022-01-18 | Ecolab Usa Inc. | Low risk chlorine dioxide onsite generation system |
US11535541B2 (en) | 2017-02-27 | 2022-12-27 | Ecolab Usa Inc. | Method for onsite production of chlorine dioxide |
US11912568B2 (en) | 2018-03-14 | 2024-02-27 | Ica Trinova, Llc | Methods of producing a gas at a controlled rate |
US11970393B2 (en) | 2018-07-05 | 2024-04-30 | Ecolab Usa Inc. | Decomposition mediation in chlorine dioxide generation systems through sound detection and control |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5110580A (en) * | 1989-09-14 | 1992-05-05 | Iolab Corporation | Method and apparatus for chlorine dioxide manufacture |
JP6162455B2 (ja) * | 2013-03-29 | 2017-07-12 | 高砂熱学工業株式会社 | 二酸化塩素ガス発生装置 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1467204A1 (de) * | 1964-02-27 | 1969-11-06 | Inventa Ag | Verfahren zur Gewinnung von Ammoniak aus einem ammoniakhaltigen Gas durch Auswaschen mit Schwefelsaeure unter Rueckfuehrung der aus dem gebildeten Ammoniumsulfat regenerierten Saeure in den Waschprozess |
US4247531A (en) * | 1979-08-13 | 1981-01-27 | Rio Linda Chemical | Chlorine dioxide generation apparatus and process |
-
1984
- 1984-09-17 US US06/651,167 patent/US4590057A/en not_active Expired - Lifetime
-
1985
- 1985-09-16 CA CA000490836A patent/CA1228714A/en not_active Expired
- 1985-09-16 AU AU47503/85A patent/AU574224B2/en not_active Ceased
- 1985-09-17 JP JP60205141A patent/JPS61183104A/ja active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1467204A1 (de) * | 1964-02-27 | 1969-11-06 | Inventa Ag | Verfahren zur Gewinnung von Ammoniak aus einem ammoniakhaltigen Gas durch Auswaschen mit Schwefelsaeure unter Rueckfuehrung der aus dem gebildeten Ammoniumsulfat regenerierten Saeure in den Waschprozess |
US4247531A (en) * | 1979-08-13 | 1981-01-27 | Rio Linda Chemical | Chlorine dioxide generation apparatus and process |
Cited By (78)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5258171A (en) * | 1990-03-28 | 1993-11-02 | Ashland Oil, Inc. | Method of producing chlorine dioxide in a gaseous stream and apparatus therefor |
US5707546A (en) * | 1991-06-17 | 1998-01-13 | Rio Linda Chemical Co., Inc. | Generation and storage of chlorine dioxide in a non-aqueous medium |
US5639559A (en) * | 1995-07-25 | 1997-06-17 | Rio Linda Chemical Company, Inc. | Preparation of chlorite |
US6051135A (en) * | 1996-02-23 | 2000-04-18 | Water Technologies Limited | Apparatus for making aqueous chlorine dioxide and apparatus for treating water with aqueous chlorine dioxide |
US5855861A (en) * | 1996-02-23 | 1999-01-05 | Water Technologies Limited | Method and apparatus for making aqueous chlorine dioxide |
US5885543A (en) * | 1997-02-11 | 1999-03-23 | Klatte; Fred | Method for producing chlorine dioxide using calcium chloride impregnated zeolite or aqueous calcium chloride |
US6458735B1 (en) | 1997-02-11 | 2002-10-01 | Fred Klatte | Method of producing chlorine dioxide using a metal chlorite and a water-retaining substance |
US6174508B1 (en) | 1997-02-11 | 2001-01-16 | Fred Klatte | Method of producing chlorine dioxide using sodium chlorite and a water-retaining substance impregnated in zeolite or in aqueous solution |
US5853689A (en) * | 1997-02-11 | 1998-12-29 | Klatte; Fred | Method for producing chlorine dioxide by activating an impregnated zeolite crystal mixture, and mixtures for performing such method |
US6635230B2 (en) | 1997-02-11 | 2003-10-21 | Fred Klatte | Method for producing chlorine dioxide |
US6379643B1 (en) | 1997-02-11 | 2002-04-30 | Fred Klatte | Method of producing chlorine dioxide using sodium chlorite and a water-retaining substance in aqueous solution |
US6605558B2 (en) | 1997-02-11 | 2003-08-12 | Fred Klatte | Composition for producing chlorine dioxide |
US6423289B1 (en) | 1997-02-11 | 2002-07-23 | Fred Klatte | Method of producing chlorine dioxide using sodium chlorate and a water-retaining substance impregnated in zeolite or in aqueous solution |
US6503419B2 (en) | 1997-02-11 | 2003-01-07 | Fred Klatte | Method of producing chlorine dioxide using sodium chlorite and a water-retaining substance impregnated in zeolite or in aqueous solution |
WO1999051332A1 (en) * | 1998-04-02 | 1999-10-14 | Vulcan Chemical Technologies, Inc. | Chlorine dioxide generator |
US5968454A (en) * | 1998-04-02 | 1999-10-19 | Vulcan Chemical Technologies, Inc. | Chlorine dioxide generator |
US6322768B1 (en) * | 1998-09-29 | 2001-11-27 | International Paper Company | Recovery of chlorine dioxide from gas streams |
US6343653B1 (en) | 1999-08-27 | 2002-02-05 | John Y. Mason | Chemical injector apparatus and method for oil well treatment |
US7407641B2 (en) * | 2000-02-22 | 2008-08-05 | Superior Plus Inc. | Method for generating chlorine dioxide |
US20050058591A1 (en) * | 2000-02-22 | 2005-03-17 | Gerald Cowley | Chlorine dioxide generator |
US7273585B1 (en) * | 2000-06-19 | 2007-09-25 | White James M | Biological fluid disposal system |
US6431279B1 (en) | 2000-07-14 | 2002-08-13 | Jacam Chemicals, L.L.C. | Process for in situ generation of chlorine dioxide in oil and gas well formations |
US6645457B2 (en) * | 2000-08-11 | 2003-11-11 | Sabre Oxidation Technologies, Inc. | Method of generating aqueous chlorine dioxide |
US6468479B1 (en) | 2000-08-11 | 2002-10-22 | Sabre Oxidation Technologies, Inc. | Chlorine dioxide generator |
US6855294B2 (en) * | 2000-11-22 | 2005-02-15 | Resonance, Inc. | Apparatus and methods for efficient generation of chlorine dioxide |
US20020061263A1 (en) * | 2000-11-22 | 2002-05-23 | Taylor Rodney D. | Apparatus and methods for efficient generation of chlorine dioxide |
US20050152811A1 (en) * | 2000-11-22 | 2005-07-14 | Taylor Rodney D. | Apparatus and methods for efficient generation of chlorine dioxide |
US6716354B2 (en) | 2001-03-08 | 2004-04-06 | Cdg Technology, Inc. | Methods of treating water using combinations of chlorine dioxide, chlorine and ammonia |
US6761872B2 (en) | 2001-03-23 | 2004-07-13 | Chemtreat, Inc. | Method for generating chlorine dioxide |
US20040232087A1 (en) * | 2001-03-23 | 2004-11-25 | Roensch L. Fred | Method for treating aqueous systems with locally generated chlorine dioxide |
US6436345B1 (en) | 2001-03-23 | 2002-08-20 | Chemtreat, Inc. | Method for generating chlorine dioxide |
US7077995B2 (en) | 2001-03-23 | 2006-07-18 | Chemtreat, Inc., | Method for treating aqueous systems with locally generated chlorine dioxide |
US20030003015A1 (en) * | 2001-03-23 | 2003-01-02 | Roensch L. Fred | Method for generating chlorine dioxide |
US20030138371A1 (en) * | 2002-01-18 | 2003-07-24 | Cdg Technology, Inc. | Method and apparatus for generating gaseous chlorine dioxide-chlorine mixtures |
US20030203827A1 (en) * | 2002-04-30 | 2003-10-30 | Cooper Andrew J. | Method of simultaneously cleaning and disinfecting industrial water systems |
US8668779B2 (en) * | 2002-04-30 | 2014-03-11 | Nalco Company | Method of simultaneously cleaning and disinfecting industrial water systems |
US20090263313A1 (en) * | 2002-06-11 | 2009-10-22 | Martens Edward M | Chlorine dioxide generation systems |
US20110052480A1 (en) * | 2002-06-11 | 2011-03-03 | Edward Max Martens | Chlorine dioxide generation systems and methods |
US20030229422A1 (en) * | 2002-06-11 | 2003-12-11 | Vulcan Chemicals | Chlorine dioxide generation systems |
US7504074B2 (en) | 2002-06-11 | 2009-03-17 | Siemens Water Technologies Corp. | Chlorine dioxide generation systems |
US20040051080A1 (en) * | 2002-09-13 | 2004-03-18 | Ica Trinova, Llc | Composition and method for producing carbon dioxide |
US7347994B2 (en) | 2002-09-13 | 2008-03-25 | Ica Trinova, Llc | Method and composition for attracting arthropods by volatilizing an acid |
US8709396B2 (en) | 2002-09-13 | 2014-04-29 | Premark Feg L.L.C. | Method and composition for attracting arthropods by volatizing an acid |
US20040126402A1 (en) * | 2002-09-13 | 2004-07-01 | Ica Trinova Llc | Method and composition for attracting arthropods by volatilizing an acid |
US7922992B2 (en) | 2002-09-13 | 2011-04-12 | Ica Trinova, Llc | Composition and method for producing carbon dioxide |
US20080138372A1 (en) * | 2002-09-13 | 2008-06-12 | Ica Trinova Llc | Method and composition for attracting arthropods by volatilizing an acid |
US7311270B2 (en) * | 2003-12-23 | 2007-12-25 | M-I L.L.C. | Device and methodology for improved mixing of liquids and solids |
US20050189081A1 (en) * | 2003-12-23 | 2005-09-01 | M-I L.L.C. | Device and methodology for improved mixing of liquids and solids |
US20070237026A1 (en) * | 2003-12-23 | 2007-10-11 | M-I L.L.C. | Methodology for improved mixing of a solid-liquid slurry |
US8496189B2 (en) | 2003-12-23 | 2013-07-30 | M-I L.L.C. | Methodology for improved mixing of a solid-liquid slurry |
US20060068029A1 (en) * | 2004-05-17 | 2006-03-30 | Mason John Y | Method of treating with chlorine dioxide |
JP2007537969A (ja) * | 2004-05-17 | 2007-12-27 | ジョン・ワイ・メイソン | 二酸化塩素を用いて処理する方法 |
WO2005115416A3 (en) * | 2004-05-17 | 2006-11-16 | John Y Mason | Method of treating with chlorine dioxide |
US7678388B2 (en) | 2004-05-17 | 2010-03-16 | Mason John Y | Method of treating with chlorine dioxide |
CN1968602B (zh) * | 2004-05-17 | 2011-08-24 | 约翰·Y·马松 | 用二氧化氯处理的方法 |
US20060021872A1 (en) * | 2004-07-29 | 2006-02-02 | Pureline Treatment Systems, Llc | Chlorine dioxide solution generator |
US7754057B2 (en) * | 2004-07-29 | 2010-07-13 | Pureline Treatment Systems, Llc | Chlorine dioxide solution generator |
US20060034750A1 (en) * | 2004-08-11 | 2006-02-16 | Water Technologies Limited | Chlorine dioxide generator and associated methods |
US20060120928A1 (en) * | 2004-11-12 | 2006-06-08 | William Annacone | Chlorine dioxide generator |
US8513176B2 (en) | 2006-08-02 | 2013-08-20 | Ch2O Incorporated | Disinfecting and mineral deposit eliminating composition and methods |
US20080032905A1 (en) * | 2006-08-02 | 2008-02-07 | Iverson Carl E | Disinfecting/mineral treating composition and methods |
US8765656B2 (en) | 2006-08-02 | 2014-07-01 | Ch2O Incorporated | Disinfecting/mineral treating composition and methods comprising a chlorite or chlorate salt |
US20110129388A1 (en) * | 2008-07-25 | 2011-06-02 | Siemens Water Technologies Corp. | Chlorine Dioxide Generation Systems and Methods |
US8784733B2 (en) | 2008-07-25 | 2014-07-22 | Evoqua Water Technologies Llc | Chlorine dioxide generation systems and methods |
US8992893B2 (en) | 2011-04-19 | 2015-03-31 | Arms Pharmaceutical, Llc | Method of inhibiting harmful microorganisms and barrier-forming composition therefor |
WO2013050774A2 (en) | 2011-10-05 | 2013-04-11 | Paradigm Flow Services Limited | Fire main cleaning apparatus and method |
US9382116B2 (en) | 2013-01-10 | 2016-07-05 | Ica Trinova, Llc | Mixtures for producing chlorine dioxide gas in enclosures and methods of making the same |
US10308533B2 (en) | 2013-03-15 | 2019-06-04 | Sabre Intellectual Property Holdings Llc | Method and system for the treatment of water and fluids with chlorine dioxide |
US10442711B2 (en) | 2013-03-15 | 2019-10-15 | Sabre Intellectual Property Holdings Llc | Method and system for the treatment of produced water and fluids with chlorine dioxide for reuse |
US20180044180A1 (en) * | 2015-03-02 | 2018-02-15 | International Dioxcide, Inc. | Method for treating water with chlorine dioxide |
WO2016140772A1 (en) * | 2015-03-02 | 2016-09-09 | The Chemours Company Fc, Llc | Method for treating water with chlorine dioxide |
US11535541B2 (en) | 2017-02-27 | 2022-12-27 | Ecolab Usa Inc. | Method for onsite production of chlorine dioxide |
US11130677B2 (en) | 2017-03-24 | 2021-09-28 | Ecolab Usa Inc. | Low risk chlorine dioxide onsite generation system |
US10850981B2 (en) | 2017-04-25 | 2020-12-01 | Ica Trinova, Llc | Methods of producing a gas at a variable rate |
US11518676B2 (en) | 2017-04-25 | 2022-12-06 | Ica Trinova Llc | Methods of producing a gas at a variable rate |
US11225421B2 (en) | 2017-08-17 | 2022-01-18 | Ecolab Usa Inc. | Low risk chlorine dioxide onsite generation system |
US11912568B2 (en) | 2018-03-14 | 2024-02-27 | Ica Trinova, Llc | Methods of producing a gas at a controlled rate |
US11970393B2 (en) | 2018-07-05 | 2024-04-30 | Ecolab Usa Inc. | Decomposition mediation in chlorine dioxide generation systems through sound detection and control |
Also Published As
Publication number | Publication date |
---|---|
JPH0362641B2 (pt) | 1991-09-26 |
JPS61183104A (ja) | 1986-08-15 |
AU4750385A (en) | 1986-03-27 |
CA1228714A (en) | 1987-11-03 |
AU574224B2 (en) | 1988-06-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4590057A (en) | Process for the generation of chlorine dioxide | |
CA1153866A (en) | Chlorine dioxide generation apparatus and process | |
KR970000479B1 (ko) | 이산화염소의 제조방법 | |
CA1339970C (en) | Process for preparing chlorine dioxide and apparatus therefor | |
AU2009328453B2 (en) | Method for treating water and aqueous systems in pipelines with chlorine dioxide | |
US20030031621A1 (en) | Process and apparatus for the generation of chlorine dioxide using a replenished foam system | |
KR100687106B1 (ko) | 이산화염소 발생기 | |
US6790427B2 (en) | Process for producing chlorine dioxide | |
RU2268241C2 (ru) | Способ получения диоксида хлора | |
DK2234927T3 (en) | PROCESS FOR THE TREATMENT OF WATER WITH Dioxide | |
US20070178021A1 (en) | Method and Apparatus for Generating Gaseous Chlorine Dioxide-Chlorine Mixtures | |
CA2337599C (en) | Chlorine dioxide generator | |
US5516501A (en) | Process for the preparation of aqueous solutions of bromine based disinfectants | |
JP2797070B2 (ja) | 連続静的二酸化塩素水の製造方法及びその装置 | |
US5597544A (en) | Preparation of chlorite | |
CA1230464A (en) | Small scale generation of chlorine dioxide for waste water treatment | |
US5639559A (en) | Preparation of chlorite | |
JPH1192104A (ja) | 高純度な二酸化塩素水性組成物、その製造方法及び製造装置 | |
JPH09156902A (ja) | 簡易二酸化塩素発生機 | |
EP0275246A2 (en) | Improved apparatus for the production of chlorine dioxide | |
JPS56114807A (en) | Preparation of highly concentrated aqueous solution of sodium hypochlorite |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: RIO LINDA CHEMICAL COMPANY, INC. 2444 ELKHORN BLVD Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:HICKS, BRUCE W.;REEL/FRAME:004312/0080 Effective date: 19840910 Owner name: RIO LINDA CHEMICAL COMPANY, INC., A CORP. OF CA,CA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HICKS, BRUCE W.;REEL/FRAME:004312/0080 Effective date: 19840910 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FEPP | Fee payment procedure |
Free format text: PAT HLDR NO LONGER CLAIMS SMALL ENT STAT AS INDIV INVENTOR (ORIGINAL EVENT CODE: LSM1); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
FPAY | Fee payment |
Year of fee payment: 12 |